Dyeing metallized polyolefin with quinoline dyes



United States Patent 3,365,264 DYEKNG METALLIZED POLYOLEFIN WITHQUINOLINE DYES Paul L. Stright, Erie County, N.Y., assignor to AliiedChemical Corporation, New York, N.Y., a corporation of New York NoDrawing. Original applications Feb. 12, 1963, Ser. No. 257,889, and Feb.28, 1963, Ser. No. 261,858, now Patent No. 3,254,072, dated May 31,1966. Divided and this application Aug. 25, 1965, Ser. No. 482,605

Claims. (Cl. 8-42) ABSTRACT OF THE DISCLOSURE Alpha-olefins having from24 carbon atoms and containing a small quantity of a Werner complexforming metal are colored in deep shades fast to light by employing awater-insoluble monoazo dyestuff derived from a diazotizedS-aminoquinoline compound and capable of forming a metal chelate withsaid metal.

This application is a divisional of my copending applications Ser.Numbers 257,889 and 261,858 filed Feb. 12, 1963 and Feb. 28, 1963,respectively, the latter having issued as U.S. Patent 3,254,072 on May31, 1966.

The present invention relates to the dyeing of a-olefin polymers. Moreparticularly, it relates to the dyeing of normally solid polymers ofa-olefins having from two to four carbon atoms and containing a smallquantity of a Werner complex forming metal. Especially, this inventionis directed to the dyeing of polypropylene containing a Werner complexforming metal or compound thereof with water-insoluble monoazo dyestuffscapable of forming a metal chelate with said metal and derived from adiazotized S-aminoquinoline compound.

Polymers of a-olefins such as ethylene and propylene have been producedin steadily increasing quantities and grades in recent years, andbecause of their many valuable characteristics of mechanical strength,high elasticity, resistance to solvents and other elements, have foundtheir way into a multitude of useful applications in the form of films,filaments, yarns, fabrics, ropes, molded products and the like. However,because of their extreme chemical inertness and hydrophobic character,these materials have shown little affinity for dyestuffs and pigmentsgenerally available for the coloration of natural and syntheticmaterials. Thus attempts to effect the coloration of poly-aolefius bycompounding pigments into the resin, as in Banbury mixers, compoundextruders, etc. were not entirely satisfactory due to the difiiculty ofobtaining adequate dispersion of the pigment. Dispersed dyestuffsproduce light to medium shades in poly-a-olefins although the fastnessto light and washing of such colorations leaves much to be desired.

The receptivity of the polymers for known classes of dyestuffs has beenimproved by grafting or otherwise introducing polymeric chainscontaining functional groups to the polyolefin. However, such measureswhile, in part, successfully add to the cost of the resulting fiber.

It has recently been disclosed to dye poly-a-olefin fibers byconventional dyeing procedures by means of aqueous emulsions of oilsoluble dyes. Such emulsions when applied to poly-a-olefin textiles inaqueous dyebaths produce light to medium shades of acceptable fastnesscharacteristics, but tend to leave a residue of the carrier oil on thegoods, which is removed with difficulty, as by drastic soaping or costlyextraction procedures.

Polymers of a-olefins, especially polypropylene, are subject todegradation on exposure to heat and light such as is encountered duringmechanical processing as for example in molding, exrtusion, etc., andduring exposure 3,365,264 Patented Jan. 23, 1968 of the finishedarticles such as rugs, draperies, automobile seat covers, to sunlight.

It is known that polymers of a-olefins and especially polypropylene canbe stabilized against degradation due to heat and light by incorporatingin the polymer various compounds, many of which are compounds, inorganicand organic, of metals, such as nickel, zinc, cobalt, copper, cadmium,titanium, aluminum, iron, zirconium, manganese, vanadium and the like.These metals belong to the transition group of elements andcharacteristically are capable of forming Werner type complex compounds.Nickel compounds such as the bis(p-alkylphenol)-monosulfide nickelcompounds disclosed in U.S. 2,971,940 and 3,006,885 and nickelacetyl-acetonate (Belgium Patent 608,408) as stabilizers forpolypropylene, are especially effective in this connection. Inorganicchromium compounds, as disclosed in French Patents 1,142,024 and1,142,025 are likewise effective in minor amounts as stabilizer forthese polymers.

These stabilizing agents are used in relatively small amounts, fromabout 0.001 to 3% by weight, and are generally incorporated in thepolymer during the processing stage. Such small amounts are generallysufficient to provide adequate stabilization of the polymer againstdegradation by heat and light, and consequently, will be those termedherein as stabilizing amounts.

It is known, further, that polymers of a-olefins are formed by reactingthe olefin monomer in the presence of metal catalysts most, if not all,of which are Werner complex forming metals. Although the. preparation ofsuch polymers generally includes a step designed to remove suchcatalysts, trace amounts, i.e. amounts of the order of 0.002 to 0.01% byweight, generally remain in the polymer product.

It is a principal object of the present invention to provide aneffective process for the coloration of normally solid polymers ofa-olefins having from 2 to 4 carbon atoms. Another object is to providea process for dyeing poly-a-olefin fibers in deep shades fast to light.A further object is to provide a process for the dyeing of polypropylenecontaining a Werner complex forming metal with water insoluble monoazodyestuffs, of the 8-azo quinoline series, containing chelatable groups.

These and other objects are accomplished according to my inventionwherein normally solid polymers of a-olefins having from 2 to 4 carbonsper unit and containing Werner complex forming metals or compoundsthereof are contacted with an aqueous dispersion of a waterinsolublemonoazo dyestuff, obtained by diazotizing 8- aminoquinoline and couplingwith a compound containing at least one group chelatable with the metal.

Chelatable azo dyestuffs are Well known in the dyestuff art. Suchdyestuffs possess a group or groups capable of binding certain metals bymeans of coordinate and covalent linkages commonly associcated withmetal chelate compounds.

The water insoluble dyestuffs useful in the process of my inventioncorrespond to the following general formula:

wherein R is the residue of an azo coupling component selected from thegroup consisting of B-naphthols, l-aryl- S-pyrazolones,hydroxydiphenylamines, 1,3-propanediones and 2,4-dihydroxyquinolines,and wherein R and the quinoline nucleus may contain substituents otherthan Water-solubilizing groups, eg SO H, such as alkyl, aryl, alkoxy,halogen, nitro, hydroxy, substituted amino, e.g.

alkylamino, arylamino, acylamino, sulfonamide, carboxyamide, cyano andtriiluorornethyl. Dyestuffs of this class are generally old in the artand are referred to as 8-azoquinoline dyestuffs or 8--quinolinyl monoazodyestuffs. They may be obtained by coupling a diazotized8-aminoquinoline compound with a suitable coupling component as definedabove.

As examples of suitable S-aminoquinoline compounds the following arementioned:

The following illustrate coupling components (R) suitable for use inpreparation of the dyestuffs utilized in my invention:

B-anilinophenol Z-naphthol 6-bromo-2-naphthol 8-acetamido-2-naphthol8-carboethoxyamino-Z-naphthol 1-phenyl-3-methyl-5pyrazolone l(2,3 or4-ohlorophenyl)-3-methyl-5-pyrazolone 1- 2,5 -dichlorophenyl -3methyl-5-pyrazolone 2,4-dihydroxyquinoline 2,4-pentanedione1,3-diphenyl-1,3-propanedione 1,3-bis(p-tolyl)-1,3-propanedione1-phenyl-2,4-pentanedione l-phenyl-1,3-butanedionel-(2-furyl)-l,3-butanedione 1,l,1-trifluoro-2,4-pentanedione6-methoxy-2-naphthol The dyeing of polypropylene and the like with dyestuffs of the aforesaid class is carried out in a manner conventional inthe dyeing of dispersed dyestuffs. These water insoluble dyes areapplied as aqueous dispersions whichcan be obtained by various knownmeans. For example, the dyestuif is ground in the presence of adispersing agent by means of a micropulverizer, sand, inorganic salt andthe like. The more finely divided the dyestuff composition is, the moreeffective as a dye the composition will be, as is generally known. Thedispersed dye is admixed with a sufiicient quantity of water to obtain athoroughly wetted paste or slurry, which then is diluted with a furtherquantity of water to obtain the desired concentration of dyestulf in theultimate dyebath. For dyeing, the polyolefin material is entered intothe dyebath, which may or may not contain the usual dyeing adjuvants,e.g. auxiliary wetting agents, etc., and the dyeing effected by heatingthe bath to a suitable dyeing temperature and working the material inthe heated bath for a sufficient period, usually about one hour, toobtain the desired depth of shade. During the latter period, theaddition of dilute acid to a pH of below 5, will result in a betterexhaustion of the dyestuff from the dyebath. The dyed material may thenbe rinsed with water, washed with warm C.) mild soap solution, rinsedagain with water and dried.

An effective mode of preparing aqueous dispersion of the 8-azoquinolinedyestuffs suitable for use in this invention, is that described incopending U.S. application Ser. No. 5,123, filed Jan. 28, 1960, now USPatent No. 3,069,220. By the novel procedure disclosed therein, themetallizable monoazo dyestufr' is firstdissolved in a watermisciblepolyhydric alcohol or ether. To this solution is added, with agitation,a surface active agent and water whereby a neutral aqueous dispersion ofthe dyestufr" in finely divided condition results. The initialdispersion may be advantageously prepared with a relatively limitedquantity of Water to produce a stable concentrated stock dispersion ofthe monoazo dyestuff. This dispersion can be used to prepare the dyebathby adding aliquot portions to water as and when desired and thepolyolefin dyed according to conventional techniques hereinabovedescribed.

The polyolefins are dyed in accordance with the process of my inventionin shades which are characterized by their fastness to light, tocrocking (or rubbing) and to wet treatments, i.e., to washing and to drycleaning.

The depth of shade obtained in my novel dyeing procedure will dependupon several factors, the most important of which are (1) The amount ofmetal present in the polymer, and (2) The ease with which the metal andchelatable dyestuif react to form the metal chelate compound.

As will be apparent, the amount of Werner complex forming metalavailable in the polymer will govern the depth of shade produced. Thus,trace amounts of such metal or compound thereof, e.g. 0.002% or morecalculated as metal by weight of polymer, will produce light or pastelshades, whereas stabilizing amounts (0.01% or more) will yield deepshades. The metal content of the polymer can be augmented by treatingthe polymer with a solution or dispersion of metal compound prior todyeing. The metal can also be added during the spinning or the likeoperation for the specific purpose of improving the dye-ability of thepolymer. Amounts of metal in excess of about 3% should not, in general,be added as such amounts may affect the physical properties of thepolymer and make it unsatisfactory for the particular use for which itis intended. In general, the range of concentration of 0.1 to 0.5% ofmetal is adequate to obtain commercially desirable shades.

The depth of shade obtained is affected also, although to a somewhatlesser extent than the metal content of the polymer, by the ease withwhich the dyestuff reacts with the metal to form the ehelate compound.

While I do not wish to be limited by any theory of the mechanism bywhich my novel procedure operates, I believe that the monoazo dyestuffforms a coordinate complex or chelate with the metal present within thepolyolefin. The result is highly surprising in view of the hydrophobiccharacter of the polymer and the well known resistance of such polymersto penetration by water and organic solvents.

The amount of dyestuff employed relative to the amount of polyolefinmaterial to be dyed can be varied over a wide range. The amount usedwill depend to a major extent upon the depth of shade desired and alsoupon the metal content of the polymer. In most instances, deep shadescan be obtained from 0.5% dyeings, which shades are increased little inintensity by increasing the dye concentration to 2.0% or more. Lightshades can be obtained by the use of as little as 0.05% or less of thedyestuff.

The chelatable 8-azoquinoline dyestuffs used in the process of myinvention have little or no solubility in the aqueous dyebath, whichpreferably is maintained at a pH of 5 or less. They are applied in theform of dispersions in the manner of the well known disperse dye class.Such dyes, it is known, are in a finely divided condition and usuallyare assisted by admixture with dispersing agents, which may be of thenon-ionic, anionic or wherein R is an alkyl group having from 12 to 22carbon atoms or an alkyl phenol residue wherein the alkyl group containsfrom 6 to 13 carbon atoms inclusive, and wherein n is at least 4 andespecially between about 6 and 40.

Examples of products in this preferred group of nonionic dispersantsinclude:

Triton X-l wherein R is the residue of iso-octylphenol and n is 7 to 9;

Triton X102 wherein R is the residue of iso-octylphenol and n is 11;

Tergitol NPX wherein R is the residue of ethylhexylphenol and n isbetween 8 and 9;

Neutronic 600 wherein R is the residue of nonylphenol and n is 9;

Emulphor ELN wherein R is the residue of dodecylphenol and n is 19.

Dispersants other than the above described group of non-ionics can beused, if desired, to assist dyeing of poly-a-olefins by the finelydivided chelatable monoazo dyestuffs. Further, mixtures of suchdispersing agents are contemplated in this connection also.

The following examples illustrate the process of my invention. Thetemperatures are given in degrees centigrade, parts and percentages areby weight unless otherwise specified.

Example 1 A monoazo dyestuff was prepared from 8-amino-quinoline in thefollowin manner. The base (14.4 g., 0.10 mole) in aqueous hydrochloricacid solution was diazotized with sodium nitrite in the usual manner andthe resulting diazo was coupled with alkaline fi-naphthol solution (18.4g., 0.105 mole fi-naphthol in 1000 mls. water containing 15 ml. of 50 B.sodium hydroxide solution and 200 g. sodium carbonate) at below C. Themonoazo compound was isolated, washed free of B-naphthol and dried.

One part of the above monoazo dyestuif was mulled with five parts ofdiethylene glycol and Triton X-100 (0.1 part) was added. After theaddition of about 4000 parts of warm (40 C.) Water, 100 parts ofHerculon Type 40 an isotactic polypropylene containing abis-(palkylphenol) monosulfide nickel compound as stabilizer in theamount of about 0.12% of nickel based on the weight of the polypropylenewere entered into the dyebath and worked therein as the bath was heatedto boiling. The dyeing was continued at the boil for about one hour. Thedyed fiber was removed from the bath and washed well with 0.25% soapsolution at 60 C. After rinsing in warm water, the dyed fiber was dried.It was colored a deep reddish-violet. The light fastness of the dyedfiber was excellent (about 80 hours in the Fade ometer). The dyed fiberwas also fast to Washing, drycleaning and crocking.

Examples 2 to 7 A series of monoazo dyestuffs were prepared from 8-aminoquinoline by diazotization and coupling with various organiccompounds. Herculon Type 40" polypropylene Was dyed as described inExample 1 above, using the 8-azoquinoline dyestuffs listed below inTable I. Deep shades of good fastness to light, washing, drycleaning andcrocking were obtained as shown below. The various polypropylene dyeingswere tested for light fastness using AATCC 16A-1960 standard test. TheAATCC ratings signify an appreciable break in color fastncss after acertain number of hours in a Fade-Ometer as follows: 2 (rating)=5 hours;3:10; 4:20; 5:40; 6:80; 7:160;

TABLE I 8-amino- Coupling Light Example qulnoline Component ShadeFeatures Compound 2 8-arninoquin- 1-phenyl-3-methy1- Orange" 5 oline. 5-yrazolone. 3 ..d0 Hy roxy-diphenyl- Bluish- 5 amine. red. 4 ..doDihydroxyquin- Red- 4 olines. brown. 5 do 2,4-pentanedione Yel1ow 4-5 6do l-phenyl-1,3-butane- -do dione. 7 6-methoxy-8- B-naphthol Violet...5-6

aminoqulnoline.

The following examples illustrate the shades which are obtained bycoloring stabilized polypropylene with dyes prepared in accordance withthe procedures of Example 1 using the various S-aminoquinoline compoundsand coupling components identified below in Table II.

It can thus be seen that a novel and eflicient method has been devisedfor the dyeing of poly-a-olefins containing a Werner complex formingmetal with monoazo dyestuffs derived from 8-amino-quinoline. As will beevident to those skilled in this art, the invention is not limited tothe details .of the foregoing purely illustrative examples and thatchanges can be made without departing from the scope or spirit of myinvention.

The presence of the Werner complex forming metal (or compound thereof)in an amount sufficient to impart a degree of stabilization of thepoly-a-olefin against degradation by heat and/or light is believednecessary to obtain all the beneficial elfects of my invention, andhence such amount, e.g. 0.01% or more are to be preferred. The amount ofsuch metal used varies widely depending upon the degree of stabilizationthe fabricator of the polymer desires to impart.

I claim:

1. A process for dyeing a normally solid polymer of an alpha olefinhaving 2 to 4 carbon atoms and containing an effective amount .of aWerner complex-forming metal dispersed therein which comprisescontacting said solid polymer with an aqueous dispersion of awater-insoluble monoazo dyestuif having the formula:

wherein R is the residue of an az-o coupling component selected from thegroup consisting of B-naphthols, l-aryl- S-pyrazolones,hydroxydiphenylamines, 1,3 propanediones and 2,4-dihydroxyquinolines andwherein the quinoline nucleus may be further substituted by non-Watersolubilizing substituents.

2. The process of claim 1 wherein said dispersion is acidic.

3. The process of claim 1 wherein said metal is present in the amount ofat least 0.01% by weight of the polymet.

4. The process of claim 1 wherein said polymer is isotacticpolypropylene.

5. The process of claim 1 wherein the pH of said aqueous dispersion isabout 5.

6. The process of claim 1 wherein said metal is nickel.

7. The process of claim 6 wherein said nickel is present in the form ofan organic chelate complex.

8. The process of claim 1 in which the monoazo dyestufi has the formula:

9. The process of claim 1 in which the monoazo dyestuff has the formula:

10. The process of claim 1 in which the monoazo dyestuif has theformula:

11. The process of claim 1 in which the monoazo dyestuff has theformula:

12. The process of claim 1 in which the monoazo dyestuff has theformula:

References Cited UNITED STATES PATENTS 8/1965 Mills et al. 8-75 I.TRAVIS BROWN, Acting Primary Examiner.

35 D. LEVY, Assistant Examiner.

